EP0411466A2 - Wärmeentwickelbares farbphotographisches lichtempfindliches Material - Google Patents

Wärmeentwickelbares farbphotographisches lichtempfindliches Material Download PDF

Info

Publication number
EP0411466A2
EP0411466A2 EP90114284A EP90114284A EP0411466A2 EP 0411466 A2 EP0411466 A2 EP 0411466A2 EP 90114284 A EP90114284 A EP 90114284A EP 90114284 A EP90114284 A EP 90114284A EP 0411466 A2 EP0411466 A2 EP 0411466A2
Authority
EP
European Patent Office
Prior art keywords
sensitive material
substituted
light
group
dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90114284A
Other languages
English (en)
French (fr)
Other versions
EP0411466A3 (en
EP0411466B1 (de
Inventor
Toshiki Fuji Photo Film Co. Ltd. Taguchi
Takayuki Fuji Photo Film Co. Ltd. Ito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0411466A2 publication Critical patent/EP0411466A2/de
Publication of EP0411466A3 publication Critical patent/EP0411466A3/en
Application granted granted Critical
Publication of EP0411466B1 publication Critical patent/EP0411466B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046

Definitions

  • This invention relates to a heat-developable color photographic light-sensitive material, and more particularly to a heat-developable color photographic light-sensitive material capable of giving positive color images having high maximum density, low minimum density and less stains.
  • Heat-developable light-sensitive materials are known in the field of art and heat-developable light-­sensitive materials and processes for processing them are described, e.g., in Shashin Kogaku no Kiso (The Basis of Photographic Engineering) , "Non-Silver Salt Photography", pages 242 to 255, published by Corona Sha, (1982).
  • the aforesaid heat-developable light-sensitive material for obtaining color images is of a non-fixing type, silver halide remains therein after forming images, which causes a serious problem that when the color images are exposed to intense light or stored for a long period of time, the background is gradually colored. Furthermore, the aforesaid processed have disadvantages that the development requires generally a relatively long period of time and images obtained have high fog and a low image density.
  • JP-A as used herein mean an "unexamined published Japanese patent application”
  • the develop­ment temperature is high and the light-sensitive materials being employed are yet insufficient in storage stability.
  • U.S. patent 4,559,290 discloses a process of using a so-called DRR compound which has been converted into an oxidized type compound having no faculty of releasing a dye and a reducing agent or a precursor therefor, oxidizing the reducing agent by heat development according to the exposed amount of silver halide and reducing the aforesaid compound with the reducing agent which remained without being oxidized to release a diffusible dye.
  • EP-A-220746 and Kokai Giho , 87-6199 (Vol. 12, No. 22) describe heat-developable color photographic light-sensitive materials using a compound capable of releasing a diffusible dye by a reductive cleavage of an N-X bond (wherein X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a compound capable of releasing a diffusible dye by the same mechanism as described above.
  • the aforesaid heat-developable color photographic light-sensitive materials giving positive color images are not in the level of commercially available color print materials in the stains, and tone reproducibility of color images formed.
  • the object of this invention is, therefore, to improve the discrimination, and tone reproducibility of a heat-developable color photographic light-sensitive material using reducible dye-providing compound(s).
  • a heat-developable color photographic light-­sensitive material comprising at least a light-sensitive silver halide, a binder, a dye-providing non-diffusible compound capable of releasing a diffusible dye on being reduced (hereinafter, the compound is referred to as a "reducible dye-providing compound”), and a reducing agent, wherein the light-sensitive material further contain at least one compound represented by following formula (I), (II), or (III); wherein R1 and R2 each represents a substituted or un­substituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted hetero­cyclic group, with a proviso that R1 and R2 each represents a group having no redox activity after its cleavage and R3 and R4 each represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl
  • the compounds shown by aforesaid formulae (I), (II), and (III) are ester or amide derivatives of oxalic acid, malonic acid, substituted malonic acid, ⁇ -keto-­acid, ⁇ -keto acid, substituted ⁇ -keto-acid, or substi­tuted ⁇ -keto-acid.
  • R1 and R2 in formulae (I), (II), and (III) each represents a substituted or unsubstituted alkyl group having preferably from 1 to 40 carbon atoms, more preferably from 1 to 20 carbon atoms (e.g., methyl, ethyl, propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-­hexyl, cyclohexyl, n-octyl, n-decyl, n-dodecyl, n-hexa­decyl, 2-ethylhexyl, decalyl, benzyl, alkylbenzyl, alkoxybenzyl, hydroxyethyl, acyloxyethyl, and alkoxy­ethyl), a substituted or unsubstituted aryl group having preferably not more than 40 carbon atoms, more preferably not more
  • R3 and R4 each represents a hydrogen atom, a halogen atom (e.g., chlorine and bromine), a substi­tuted or unsubstituted alkyl group, a substituted or un­substituted aryl group, or a substituted or unsubsti­tuted heterocyclic group, each group having preferably not more than 20 carbon atoms, more preferably not more than 8 carbon atoms and examples thereof being those as described above for R1 and R2.
  • a halogen atom e.g., chlorine and bromine
  • the amount thereof is from 0.01 to 10 mole times, and preferably from 0.05 to 2 mole times the total amount of the reducing agent.
  • the compound may exist in the light-­sensitive layer(s), intermediate layer(s), or a protective layer of the light-sensitive material.
  • the compound may exist in one layer or in two or more layers.
  • the compound shown by formula (I), (II), (III) is preferably used by coemulsifying a mixture of the compound with the same high-boiling organic solvent as that used in case of dispersing a reducible dye-­providing compound and/or an electron donor in a hydrophilic binder as described below, together with the reducible dye-providing compound and/or the electron donor.
  • the compound shown by formula (I) or (II) is more preferably coemulsified with the reducible dye­providing compound and/or the electron donor.
  • one unit of light-sensitive layer is composed of a combination of the reducible dye-­providing compound, an electron transfer agent, an electron donor, a binder, and a silver halide emulsion.
  • the reducible dye-providing compound may exist in the layer of a silver halide emulsion but may exist in a layer adjacent to the silver halide emulsion layer. In the latter case, it is preferred in the point of sensitivity that the layer containing the reducible dye-­providing compound is disposed under the silver halide emulsion layer.
  • the electron transfer agent and the electron donor may exist in either the silver halide emulsion layer or the layer containing the reducible dye-providing compound.
  • each light-sensitive layer is composed of two or more layers.
  • the reducible dye-providing compound being used in this invention is preferably a compound shown by the following formula (C-I) PWR - (Time) t - Dye (C-I) wherein PWR represents a group releasing -(Time) ⁇ Dye by being reduced; Time represents a group releasing Dye through a subsequent reaction after being released from PWR as -(Time) ⁇ Dye; t represents 0 or 1; and Dye represents a dye or a precursor thereof.
  • PWR may be one corresponding to a moiety containing the electron acceptive center and the intramolecular nucleophilic substitution reaction center in a compound capable of releasing a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in U.S. Patents 4,139,389, 4,139,379, and 4,564,577, JP A-59-­185333 and JP-A-57 84453, or may be one corresponding to a moiety containing the electron acceptive quinoid center and the carbon atom bonding the quinoid center to a photographic reagent in a compound capable of releasing the photographic reagent by an intramolecular electron transfer reaction after being reduced as disclosed in U.S. patent 4,232,107, JP-A-59-101649 and JP-A-61-88257, RD , No. 24025, IV, (1984).
  • PWR may be one corresponding to a moiety containing the aryl group substituted by an electron attractive group and the atom (a sulfur atom, a carbon atom, or a nitrogen atom) bonding the aryl group to a photographic reagent in a compound capable of releasing the photographic reagent by the cleavage of a single bond after being reduced as disclosed in JP-A-56-142530 and U.S. Patents 4,343,893 and 4,619,884, it may be one corresponding to a moiety containing the nitro group and the carbon atom bonding the nitro group to a photo­graphic reagent in a nitro compound capable of releasing the photographic reagent after receiving electron as disclosed in U.S.
  • PWR there may be a compound having SO2-X (wherein X represents oxygen, sulfur or nitrogen) and an electron attractive group in the molecule as disclosed in U.S. Patent 4,840,887 and JP-A-­62-106885, a compound having PO-X (wherein X has the same significance as above) and an electron attractive group in the molecule as disclosed in Japanese Patent Application No. 62-106895 (corresponding to JP-A-63-­271344) and a compound having C-X′ (wherein X′ repre­sents oxygen, sulfur, nitrogen, or -SO2-) and an electron attractive group in the molecule as disclosed in Japanese Patent Application No. 62-106887 (corre­sponding to JP-A 63-271341).
  • Dye is bonded to at least one of R101, R102, and EAG.
  • X represents an oxygen atom (-O-), a sulfur atom (-S-), or a nitrogen-containing group (-N(R103) ⁇ ).
  • R101, R102, and R103 each represents a group other group than hydrogen atom or a simple bond.
  • R101, R102, and R103 there are an alkyl group, an aralkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, etc., and these groups may have a substituent.
  • R101 and R103 each is preferably an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group each of which may be substituted or unsubstituted. Also, the carbon atom number of each group shown by R101 and R103 is preferably not more than 40.
  • R102 is preferably a substituted or un­substituted acyl group or a substituted or unsubstituted sulfonyl group.
  • the carbon number of the group shown by R102 is preferably not more than 40.
  • R101, R102 and R103 may combined with each other to form a 5- to 8-membered ring.
  • X is particularly preferably oxygen.
  • (Time) ⁇ is bonded to at least one of R104 and EAG.
  • X has the same meaning as above.
  • R104 represents an atomic group forming a 5- to 7-membered monocyclic or condensed heterocyclic ring containing the nitrogen atom by combining with X and the nitrogen atom.
  • EAG represents a group capable of accepting an electron from a reducing substance and is bonded to the nitrogen atom.
  • EAG is preferably a group shown by the following formula (A); wherein Z1 represents - -Sub or - - and V n represents an atomic group forming a 3- to 8-membered aromatic group and n represents an integer of from 3 to 8.
  • V3 is -Z3-
  • V4 is -Z3-Z4-
  • V5 is -Z3-Z4- Z5-
  • V6 is -Z3-Z4-Z5-Z6-
  • V7 is -Z3-Z4-Z5-Z6-Z7-
  • V8 is -Z3-Z4-Z5-Z6-Z7-Z8-.
  • Z2 to Z8 each is -O-, -S-, or -SO2- (wherein Sub represents a simple bond ( ⁇ -bond), a hydrogen atom or the substituent shown below.
  • the Sub(s) may be the same or different, and may combine with each other to form a 3- to 8-membered saturated or unsaturated carbon ring or heterocyclic ring.
  • Sub(s) are selected such that the total sum of the Hammett's substituent constants ⁇ -para of the substituents is preferably at least +0.50, more preferably at least +0.70, and most preferably at least +0.85.
  • EAG is preferably an aryl or heterocyclic group substituted by at least one electron attractive group.
  • the substituents bonded to the aryl group or the hetero­cyclic group of EAG can be utilized for controlling the properties of the whole compound. Examples of the properties of the whole compound are the acceptability of electron as well as the water-solubility, the oil-­solubility, the diffusibility, the sublimability, the melting point, the dispersibility for a binder such as gelatin, etc., the reactivity for a nucleophilic group, and the reactivity for an electrophilic group.
  • Time represents a group capable of releasing Dye via the subsequent reaction by the cleavage of a nitrogen-oxygen bond, a nitrogen-nitrogen bond, or a nitrogen-sulfur bond with a trigger.
  • the dyes shown by Dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, etc.
  • these dyes can be used in the form of being temporarily shifted to a shorter wavelength side, which can be recolored at development.
  • the dyes disclosed in EP-A-76492 and JP-A-59-165054 can be utilized. It is necessary that the compound shown by the aforesaid formula (C-II) or (C-III) is immobile in a photographic layer and for the purpose it is preferred that the compound has a ballast group having 8 or more carbon atoms at the position of EAG, R101, R102, R104, or X (in particular, at the position of EAG).
  • the amount of the dye-providing compound depends upon the extinction coefficient of the dye but is usually from 0.05 to 5 mmoles/m2, and preferably from 0.1 to 3 mmoles/m2.
  • the dye-providing compounds can be used singly or as a combination thereof.
  • two or more kinds of dye-­providing compounds each releasing a mobile dye each having a different color can be used as a mixture thereof in such a manner that a mixture of, for example, at least one kind of a cyan dye-providing compound, at least one kind of a magenta dye-providing compound, and at least one kind of a yellow dye-providing compound is incorporated in a layer containing silver halide or a layer adjacent to the silver halide-containing layer as described in JP-A-60-162251.
  • a non-­diffusible reducing agent it is preferred to use a non-­diffusible reducing agent together with a mobile reducing agent.
  • an electron donor and an electron transfer agent ETA are used and details of these compounds are described in EP-A-220746 and Kookai Giho , No. 87-6199.
  • Particularly preferred electron donors are the compounds represented by following formula (C) or (D).
  • A101 and A102 each represents a hydrogen atom or a protective group for a phenolic hydroxy group, said protective group being releasable by a nucleophilic reagent.
  • nucleophilic reagent there are anionic reagents such as OH ⁇ , RO ⁇ (wherein R represents an alkyl group or an aryl group), hydroxamic acid anions, SO3 2 ⁇ , etc., and compounds having a non-­covalent electron pair, such as primary or secondary amines, hydrazines, hydroxylamines, alcohols, thiols, etc.
  • anionic reagents such as OH ⁇ , RO ⁇ (wherein R represents an alkyl group or an aryl group), hydroxamic acid anions, SO3 2 ⁇ , etc.
  • compounds having a non-­covalent electron pair such as primary or secondary amines, hydrazines, hydroxylamines, alcohols, thiols, etc.
  • A101 and A102 are a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a diarylphosphoryl group, and the protective groups disclosed in JP-A-59-197037 and JP-A-59-20105. Also, if possible, A101 and A102 may combine with R201, R202, R203 and R204 to form a ring. Furthermore, A101 and A102 may be the same or different.
  • R201, R202, R203 and R204 each represents a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amido group, an imido group, a carboxy group, a sulfonamido group, etc. These groups may, if possible, have a substituent.
  • R201, R202, R203, and R204 are at least 8. Also, in formula (C), R201 and R202 and/or R203 and R204 may combine with each other to form a saturated or unsaturated ring and in formula (D), R201 and R202, R202 and R203, and/or R203 and R204 may combine with each other to form a saturated or unsaturated ring.
  • R201 to R204 are substituents (groups) other than hydrogen atom.
  • at least one of R201 and R202 and at least one of R203 and R204 are substituents other than hydrogen atom.
  • the electron donors may be used as a combination thereof or the electron donor may be used together with the precursor of it. Also, the electron donor may be the same compound as the reducing substances for use in this invention.
  • the electron donor and/or precursor thereof are preferably used as a reudcing agent.
  • the electron donor (or the precursor thereof) can be used in a wide amount range but is preferably in the range of from 0.01 to 50 moles, and more preferably from 0.1 to 5 moles per mole of the positive dye­providing compound. Also, the amount thereof is from 0.001 to 5 moles and preferably from 0.01 to 1.5 moles per mole of silver halide.
  • any compounds which are oxidized by silver halide and the oxidation products of which have a faculty of cross-oxidizing the aforesaid electron donor can be used but the compound is preferably mobile.
  • ETA are the compounds represented by following formula (X-I) or (X-­II).
  • R represents an aryl group and R301, R302, R303, R304, R305, and R306, which may be the same or different, each represents a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, each of which may be substituted.
  • R301, R302, R303, and R304 each is preferably a hydrogen atom, an alkyl group having from 1 to 10 carbon atoms, a substituted alkyl group having from 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group, and each is more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group or a phenyl group substituted by a hydroxy group, an alkoxy group, a sulfo group, a carboxy group, etc.
  • the ETA precursor for use in this invention is a compound which does not have a developing action during the preservation of the light-sensitive material before use but releases first ETA by the action of a proper activator (e.g., a base, a nucleophilic agent, etc.) or the action of heat, etc.
  • a proper activator e.g., a base, a nucleophilic agent, etc.
  • the ETA precursor for use in this invention does not have a function as ETA before development since the reaction functional group of ETA is blocked by a blocking group but functions as ETA under an alkaline condition or by heating since in this case, the blocking group is cleaved.
  • ETA precursor for use in this invention there are 1-phenyl-3-pyrazolidinone-2-acyl derivatives, 1-phenyl-3-pyrazolidinone-3-acyl derivatives, 2-­aminoalkyl derivatives, 2-aminohydroxyalkyl derivatives, metal salts (lead salts, cadmium salts, calcium salts, barium salts, etc.) of hydroquinone, catechol, etc., halogenated acyl derivatives of hydroquinone, oxazine or bisoxazine derivatives of hydroquinone, lactone-type ETA precursors, hydroquinone precursors having a quaternary ammonium group, cyclohex-2-ene-1,4-dione type compounds, compounds releasing ETA by an electron transfer reaction, compounds releasing ETA by an intramolecular nucleophilic substitution reaction, ETA precursors blocked by a phthalide group, and ETA precursors blocked by an indomethyl group.
  • the ETA precursors for use in this invention are known compounds such as the developer precursors described in U.S. Patents 3,767,704, 3,241,967, 3,246,988, 3,295,978, 3,462,266, 3,586,506, 3,615,439, 3,650,749, 4,209,580, 4,330,617, and 4,310,612, British Patents 1,023,701, 1,231,830, 1,258,924, and 1,346,920, JP-A-57-40245, JP-A-58-1139, JP-A-58-1140, JP-A-59-­178458, JP-A-59-182449 and JP-A-59-182450.
  • precursors of 1-phenyl-3-­pyrasolidinones described in JP-A-59-178458, JP-A-59-­182449, and JP-A-59-182450 are preferred.
  • ETA can be used together with the ETA precursor.
  • the combination of the electron dodonor and ETA is preferably incorporated in the heat-developable color photographic light-sensitive material.
  • the electron donors, ETA(s), and the precursors of them each can be used as a combination of two or more kinds thereof and they can be added to each of the emulsion layers (a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer, an infrared-sensitive emulsion layer, an ultraviolet-sensitive emulsion layer, etc.) of the light-sensitive material, may be added to specific emulsion layers only, may be added to a layer adjacent to an emulsion layer (an antihalation layer, a subbing layer, an interlayer, a protective layer, etc.), or may be added to all the layers.
  • the emulsion layers a blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer, an infrared-sensitive emulsion layer, an ultraviolet-sensitive emulsion layer, etc.
  • the light-sensitive material may be added to specific emulsion layers only
  • the electron donor and ETA or the ETA precursor can be added to a same layer or can be added separately to separate layers.
  • the reducing agent and the dye-providing compound may be added to a same layer or separate layers but it is preferred that the non-­diffusible electron donor exists in the layer containing the dye-providing compound.
  • ETA can be incorporated in an image-receiving material (dye-fixing layer) and when a slight amount of water exists at heat development, ETA may be dissolved in the water.
  • the preferred amounts of the electron donor and ETA or the precursors of them are, as the total amounts, from 0.01 to 50 moles, and preferably from 0.1 to 5 moles per mole of the dye-providing compound, and also from 0.001 to 5 moles, and preferably from 0.01 to 1.5 moles, per mole of silver halide.
  • the amount of ETA is not more than 60 mole%, and more preferably not more than 40 mole% of the whole reducing agent.
  • the concentration of ETA is preferably from 10 ⁇ 4 mole/liter to 1 mole/liter.
  • a high-boiling organic solvent For introducing the reducing substance, the dye-­providing compound, the electron donor, the electron transfer agent, the precursors of them, and other hydrophobic additives to a hydrophilic colloid layer, a high-boiling organic solvent may be used.
  • phthalic acid alkyl esters e.g., dibutyl phthalate and dioctyl phthalate
  • phosphoric acid esters e.g., diphenyl phosphate, triphenyl phosphate, tricyclohexyl phosphate, tricresyl phosphate, and dioctylbutyl phosphate
  • citric acid esters e.g., tributyl acetyl­citrate
  • benzoic acid esters e.g., octyl benzoate
  • alkylamides e.g., diethyllaurylamide
  • fatty acid esters e.g., dibutoxy succinate and dioctyl azerate
  • trimesinic acid esters e.g., tributyl trimesinate
  • JP-A-63-­85633 corresponding to JP-A-63-­85633
  • JP-A-59-178451 JP-A-59-178452
  • JP-A-59-178453 JP-A-59-178453
  • JP-A-59-178457 JP-A-59-178457
  • the method described in U.S. Patent 2,322,027 may be employed, or the aforesaid materials may be added to the aqueous hydrophilic colloid solution as a solution in a low-boiling organic solvent having a boiling point of from about 30°C to about 160°C.
  • a low-boiling organic solvent having a boiling point of from about 30°C to about 160°C.
  • the low-boiling solvent are lower alkyl acetates (e.g., ethyl acetate and butyl acetate), ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, ⁇ -ethoxy ethyl acetate, methylcellosolve acetate, and cyclohexanone.
  • the low-boiling organic solvent may be removed by ultra-­filtration, etc.
  • the amount of the high-boiling organic solvent being used in the aforesaid case is not more than 10 g, and preferably not more than 5 g per gram of the dye-­providing compound being used. Also, the amount thereof is not more than 5 g, and preferably not more than 2 g per gram of the non-diffusible reducing agent and further the amount thereof is not more than 1 g, preferably not more than 0.5 g, and more preferably not more than 0.3 g per gram of the binder.
  • JP-B-51-39853 the term "JP-B” as used herein means an "unexamined published Japanese patent application”
  • JP-A-51-59943 can be used.
  • the aforesaid materials may be directly dispersed in an emulsion, or after dissolving them in water or an alcohol the solution may be dispersed in an aqueous gelatin solution or an emulsion.
  • the compounds When the compounds are substantially insoluble in water, the compounds can be dispersed in a binder as fine particles in addition to the aforesaid methods as described, e.g., in JP-A-59-174830, JP-A-53-102733 and Japanese Patent Application 62-106882 (corresponding to JP-A 63-271339).
  • the heat-developable light-sensitive material has fundamentally a light-sensitive silver halide, a binder, a reducing agent, and a reducible dye-providing compound on a support and further, if possible, the light-sensitive material can contain an organic metal salt oxidizing agent.
  • the reducing agent is preferably incorporated in the heat-developable light-sensitive material but may be supplied from outside of the light-sensitive material, e.g., by a method that the reducing agent is diffused into the light-sensitive material from a dye-fixing material as will be described below.
  • a combination of at least three silver halide emulsion layers each having a light sensitivity in each different spectral region may be used.
  • the light-sensitive emulsion layers can be disposed in the disposition order usually employed for ordinary-type color photographic light-­sensitive materials.
  • each light-sensitive layer may be, if desired, composed of two or more layers.
  • the heat-developable light-sensitive material of this invention can have various subsidiary layers such as a protective layer, a subbing layer, an interlayer, a yellow filter layer, an antihalation layer, a back layer, etc.
  • silver chloride As the silver halide being used in this invention, there are mentioned silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.
  • the silver halide emulsion for use in this invention may be of a surface latent image type or an internal latent image type.
  • the internal latent image type silver halide emulsion is used as a direct reversal silver halide emulsion by combining with a nucleating agent or a light fogging process.
  • a so-called core/shell type silver halide emulsion wherein the inside of the silver halide grain has a different composition than that of the surface of the silver halide grain may be used.
  • the silver halide emulsion may be a monodisperse silver halide emulsion, a polydisperse silver halide emulsion, or a mixture of monodisperse silver halide emulsions.
  • the grain sizes of the silver halide grains for use in this invention are preferably from 0.1 to 2 ⁇ m, and particularly preferably from 0.2 to 1.5 ⁇ m.
  • the crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular of a high aspect ratio, etc.
  • the silver halide emulsion may be used as a primitive emulsion but is usually chemically sensitized.
  • a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method, etc. which are known for ordinary photographic light-sensitive materials can be used singly or as a combination thereof.
  • These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound as disclosed in JP-A-62-253159.
  • the coating amount of the light-sensitive silver halide for use in this invention is in the range of from 1 mg/m2 to 10 g/m2 calculated as silver.
  • an organic metal salt can be used together with the light-sensitive silver halide as an oxidizing agent.
  • an organic silver salt is particularly preferably used.
  • organic silver salt oxidizing agent As an organic compound capable of use for forming the aforesaid organic silver salt oxidizing agent, there are benzotriazoles described in U.S. patent 4,500,626, Columns 52 to 53, fatty acids, etc. Also, the silver salts of carboxylic acids having an alkyl group, such as phenyl propiolic acid silver described in JP-A-60-113235 and acetylene silver described in JP-A-­61-249044 are useful as the organic silver salt oxidizing agent. Organic silver salts may be used singly or as a mixture thereof.
  • the organic silver salt can be used in an amount of from 0.01 to 10 moles, and preferably from 0.01 to 1 mole per mole of the light-sensitive silver halide.
  • the sum of the proper coating amounts of the light-sensitive silver halide and the organic silver salt is from 50 mg/m2 to 10 g/m2 calculated as silver.
  • various antifoggants or photographic stabilizers can be used. Examples of them are azoles and azaindenes described in RD , No. 17643, pages 24 to 25 (1978), nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, mercapto compounds and the metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957.
  • the silver halide for use in this invention may be spectrally sensitized by methine dyes and the like.
  • the dyes for the spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • sensitizing dyes may be used singly or as a combination thereof and a combination of sensitizing dyes is frequently used for the purpose of super-­sensitization.
  • the silver halide emulsion may contain a dye which has no spectral sensitizing action by itself and shows a supersensitization in the presence of a sensitizing dye or a compound which does not substan­tially absorb visible light and shows a super­sensitization in the presence of a sensitizing dye as described in U.S. Patent 3,615,641 and JP-A-63-23145.
  • the sensitizing dye(s) may be added to the silver halide emulsion at, before, or after the chemical ripening thereof, or before or after the nucleus formation of the silver halide grains as disclosed in U.S. Patents 4,183,756 and 4,225,666.
  • the addition amount of the sensitizing dye is from about 1 ⁇ 10 ⁇ 8 to 1x10 ⁇ 2 mole per mole of the silver halide.
  • a hydro­philic binder is preferably used as the binder for layers constituting the light-­sensitive material and dye-fixing material and examples of the binder are described in JP-A-62-253159, pages 26 to 28.
  • a transparent or translucent hydrophilic binder is preferred and examples thereof are natural compounds such as proteins (e.g., gelatin and gelatin derivatives), cellulose derivatives, and polysaccharides (e.g., starch, gum arabic, dextran, and pluran) and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc.
  • proteins e.g., gelatin and gelatin derivatives
  • polysaccharides e.g., starch, gum arabic, dextran, and pluran
  • synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers, etc.
  • high water-absorptive polymers described in JP-A-62-245260 that is a homopolymer of a vinyl monomer having -COOM or -SO3M (wherein M is a hydrogen atom or an alkali metal) and a copolymer of the aforesaid vinyl monomers or of the aforesaid vinyl monomer and other vinyl monomer (e.g., sodium methacrylate, ammonium methacrylate, and Sumika Gel L-­ 5H, trade name, made by Sumitomo Chemical Company, Limited) can be used.
  • These binders may be used as a combination thereof.
  • the absorption of water can be quickened by using the aforesaid high water-absorptive polymer.
  • the high water-absorptive polymer is used for the dye-fixing layer and a protective layer, the re-­transfer of dye(s) from a dye-fixing material to other material after transferring is prevented.
  • the coating amount of the binder is preferably not more than 20 g, more preferably not more than 10 g, and particularly preferably not more than 7 g per square meter of the light-sensitive material.
  • the layers (including a back layer) constituting the light-sensitive material or the dye-fixing material can contain various polymer latexes for improving the film properties such as the dimensional stability, the curling prevention, the sticking prevention, the cracking prevention of layers, the prevention of the occurences of pressure sensitization or desensitization.
  • Polymer latexes are described in JP-A-62-245258, JP-A-62-136648, and JP-A-62-110066.
  • a compound capable of activating the development and also stabilizing the images formed can be used for the light-sensitive material.
  • Practical examples of the preferred compound are described in U.S. Patent 4,500,626, columns 51 to 52.
  • dye-fixing material is used together with the light-sensitive material.
  • the dye-fixing material and the light-sensitive material may be a form of being formed on separate supports or a form of being formed on the same support.
  • the dye-fixing material which is preferably used in this invention has at least one layer containing a mordant and a binder.
  • Mordants which are known in the field of photography can be used in this invention. Practical examples of the mordant are described in U.S. Patent 4,500,626, column 58 to 59 and JP-A-61-88256, pages 32 to 41 and particularly preferred examples thereof are described in JP-A-62-244043 and JP-A-62-­244036.
  • the dye-acceptive high molecular compounds described in U.S. Patent 4,463,079 can be also used in this invention.
  • the dye-fixing material can have, if necessary, auxiliary layers such as a protective layer, a releasing layer, a curling prevention layer, etc.
  • auxiliary layers such as a protective layer, a releasing layer, a curling prevention layer, etc.
  • the formation of a protective layer is useful.
  • a high-boiling organic solvent can be used as a plasticizer, slipping agent, or an agent for improving the releasing property of the dye-fixing material from the light-sensitive material.
  • Practical examples of the solvent are described in JP-A-62-253159, page 25 and JP-A-62-245253.
  • various silicone oils dimethylsilicone oil and other modified silicone oils by introducing various organic groups to dimethyl siloxane
  • silicone oils dimethylsilicone oil and other modified silicone oils by introducing various organic groups to dimethyl siloxane
  • examples thereof are various modified silicone oils described in Modified Silicone Oil , Technical Material P6-18B, published by Shin-Etsu Silicone K.K. and, in particular, carboxy-­modified silicone (trade name, X-22-3710), etc.
  • silicone oils described in JP-A-62-­215953 and JP A-63-46449 are effectively used in this invention.
  • a discoloration inhibitor may be used.
  • the discoloration inhibitor there are, for example, antioxidants, ultraviolet absorbents, and a certain kind of metal complexes.
  • antioxidants examples include chroman series compounds, coumaran series compounds, phenol series compounds (e.g., hindered phenols), hydroquinone deriva­tives, hindered amine derivatives, and spiroindane series compounds. Also, the compounds described in JP-­A-61-159644 are effective.
  • Examples of the ultraviolet absorbent are benzotriazole series compounds as described in U.S. Patent 3,533,794, etc., 4-thiazolidone series compounds as described in U.S. Patent 3,352,681, etc., benzo­phenone series compounds as described in JP-A-46-2784, etc., and the compounds described in JP-A-54-48535, JP-­A-62-136641, JP-A-61-88256, etc. Also, the ultraviolet absorptive polymers described in JP-A-62-260152 are effective.
  • the discoloration inhibitor may be previously incorporated in the dye-­fixing material or may be supplied to the dye-fixing material from outside such as from the light-sensitive material.
  • the aforesaid antioxidant, ultraviolet absorbent and metal complex may be used as a combination of them.
  • a brightening agent may be used for the light-sensitive material and the dye-fixing material.
  • the brightening agent exists in the dye-fixing material or is supplied from outside such as from the light-sensitive material, etc.
  • a combination of the brightening agent and the discoloration inhibitor can be also used in this invention.
  • hardening agents which are used for layers constituting the light-sensitive material and the dye-­fixing material, there are hardening agents described in U.S. Patent 4,678,739 (column 41), JP-A-59-116655, JP-A-­62-245261 and JP-A-61-18942.
  • aldehyde series hardening agents (formaldehyde, etc.), aziridine series hardening agents, epoxy series hardening agents etc.), vinylsulfone series hardening agents [N,N′-­ethylene-bis(vinylsulfonylacetamido)ethane, etc.], N-­ methylol series hardening agents (dimethylolurea, etc.), and high molecular hardening agents (the compounds described in JP-A 62-234157, etc.).
  • the layers constituting the light-sensitive material or the dye-fixing material may contain various surface active agents as coating aids or for the purposes of improving releasability and slipping property, imparting antistatic properties and accelerat­ing development.
  • surface active agents are described in JP-A-62-173463 and JP-A-62-183457.
  • the layers constituting the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purposes of improving slipping property, static prevention, improving releasability, etc.
  • organic fluoro compound examples include the fluorine series surface active agents described in JP-B-57-9053, columns 8-17, JP-A-61-20944 and JP-A-­62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds (e.g., fluorine oil) and solid fluorine compound resins (e.g., tetrafluoroethylene resin).
  • hydrophobic fluorine compounds such as oily fluorine compounds (e.g., fluorine oil) and solid fluorine compound resins (e.g., tetrafluoroethylene resin).
  • a matting agent can be used in the light­sensitive material and dye-fixing material.
  • the matting agent there are silicon dioxide, the compounds described in JP-A-61-88256 (page 29), such as polyolefin and polymethacrylate and the compounds described in Japanese Patent Application Nos. 62-110064 and 62-110065 (corresponding to JP-A-63-274944 and JP-A-­63-274952, respectively), such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
  • the layers constituting the light-­sensitive material and the dye-fixing material may further contain a thermal solvent, a defoaming agent, an antibacterial antifungal agent, colloidal silica, etc. Practical examples of these additives are described in JP-A-61-88256, pages 26 to 32.
  • An image formation accelerator has functions of accelerating the oxidation reduction reaction of the silver salt oxidizing agent and the reducing agent, accelerating the reaction of forming dyes from the dye-providing compounds, decomposing dye, or releasing diffusible dyes, and accelerating the transfer of dyes from the light-sensitive layers to the dye-fixing layer.
  • the image formation accelerators are classified into bases or base precursors, nucleophilic compounds, high-­ boiling organic solvents (oils), thermal solvents, surface active agents, compounds having a co-action with silver or silver ions, etc. These substances generally have composite functions and usually have two or more of the aforesaid acceleration effects. Details thereof are described in U.S. Patent 4,678,739, columns 38 to 40.
  • the base precursor there are mentioned a salt of a base and an organic acid causing decarboxyla­tion by heat and compounds capable of releasing amines by an intramolecular nucleophilic substitution reaction, a Lossen rearrangement, or a Beckmann rearrangement. Practical examples thereof are described in U.S. Patent 4,511,493 and JP-A-62-65038.
  • the combination of sparingly water soluble metal compounds and compounds capable of causing a complex-­forming reaction with the metal ions forming the sparingly water-soluble compounds described in EP-A-­210660 and U.S. Patent 4,740,445 and the compound of forming a base by electrolysis described in JP-A-61-­232451 can be used as the base precursors.
  • the former method is effective.
  • the sparingly water-soluble metal compound and the complex-forming compound are separately incorporated in the light-­sensitive material and the dye-fixing material, respectively.
  • various development stopping agents can be used for always obtaining constantly stable images to the deviations of the processing temperature and the processing time at development.
  • the development stopping agent is a compound capable of quickly neutralizing a base or quickly reacting with the base after the appropriate development to reduce the concentration of the base in the layer(s) and to stop the development, or a compound capable of causing a co-action with silver and a silver salt to restrain the development.
  • the development stopping agent is an acid precursor releasing an acid by heating, an electrophilic compound causing a substitution reaction with a co-existing base by heating, a nitrogen-­ containing heterocyclic compound, a mercapto compound, and precursors thereof. Details of these compounds are described in JP-A-62-253159, pages 31 to 32.
  • the material is generally a paper and a synthetic polymer (film).
  • the support are films of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (e.g., triacetyl cellulose), etc., the aforesaid films containing a pigment such as titanium oxide, etc., synthetic papers formed by polypropylene, etc., papers made of a mixture of a synthetic resin pulp such as polyethylene and a natural pulp, Yankee papers, baryta-coated papers, resin-coated papers (cast coating papers), metal sheets, cloths, glass sheets, etc.
  • the paper support, etc. can be used as it is or as a coated paper one surface or both the surfaces of which are coated with a synthetic polymer such as polyethylene, etc.
  • the surface of the support may be coated with a mixture of a hydrophilic binder, a semiconductive metal oxide such as an alumina sol and tin oxide, and an antistatic agent such as carbon black, etc.
  • a method of imagewise exposing the light-­sensitive material there are mentioned a method of directly photographing a scene, a person, etc., using a camera, etc., a method of exposing through a reversal film or a negative film using a printer or an enlarger, etc., a method of scanning-exposing an original through a slit, etc., using an exposure device of a copying machine, a method of exposing to light emitted from a light emitting diode or laser through electric signals according to an image information, and a method of displaying an image information on an image display device such as CRT (cathod ray tube), a liquid crystal display, an electroluminescence display, a plasma display, etc., and exposing to the displayed images directly or through an optical system.
  • CTR cathod ray tube
  • liquid crystal display an electroluminescence display
  • plasma display etc.
  • a light source for recording images to the light-sensitive material there are natural light, a tungsten lamp, a light emitting diode, a laser light source, and a CRT light source, etc., as described in U.S. patent 4,500,626, column 56.
  • the image-exposure can be applied by using a wavelength conversion element composed of a combination of a non-linear optical material and a coherent light source such as laser light, etc.
  • the non-linear optical material is a material capable of giving a non-linearity between the polarization and the electric field appearing on applying a strong photoelectric field such as laser light and examples of the material are inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate, BaB2O4, etc.; urea derivatives; nitroaniline derivatives; nitro­pyridine-N-oxide derivatives such as 3-methyl-4-­nitropyridine-N-oxide (POM), and the compounds described in JP-A-61-53462 and JP-A-62-210432.
  • a single crystal light waveguide type form, a fiber type form, etc. are known and they are all useful.
  • an image signal obtained from a video camera, electron still camera, etc. a television signal such as Nippon Television Signal Code (NTSC), an image signal obtained by dividing an original into many dots by scanner, etc. and an image signal made by using a computer such as CG and CAD.
  • NTSC Nippon Television Signal Code
  • the light-sensitive material and/or the dye-­fixing material may be in the form of having a conductive exothermic layer as a heating means for the heat development or the diffusion transfer of dyes.
  • a conductive exothermic layer as a heating means for the heat development or the diffusion transfer of dyes.
  • the transparent or opaque exothermic elements described in JP-A-61-145544 can be utilized.
  • the conductive layer also functions as an antistatic layer.
  • the heating temperature for the heat development step is from about 50°C to about 250°C, and particularly usefully from about 80°C to about 180°C.
  • the diffusion transfer step of dyes may be carried out simultaneously with the heat development or after finishing the heat development step.
  • the heating temperature for transferring dyes in the transfer step may be in the range of from room temperature to a temperature in the heat development step but heating temperature is preferably in the range of from about 50°C to a temperature of about 10°C lower than the temperature in the heat development step.
  • the transfer of dyes may occur by heat only but for accelerating the transfer of dyes, a solvent may be used.
  • the heating temperature is preferably from 50°C to the boiling point of the solvent.
  • the heating temperature is preferably from 50°C to 100°C.
  • Examples of the solvent which is used for accelerating the development and/or transferring diffusible dyes to the dye-fixing layer are water and a basic aqueous solution of an inorganic alkali metal salt or an organic base (as the base, those described above on the image formation accelerators can be used).
  • a low-boiling solvent or a mixture of a low-boiling solvent and water or the basic aqueous solution can be used.
  • the solvent may contain a surface active agent, an antifoggant, a sparingly water-soluble metal salt, a complex-forming compound, etc.
  • the solvent can be used in a method of being applied to the dye-fixing material and/or the light-­sensitive material.
  • the amount of the solvent may be small such as an amount of not more than the weight of the solvent corresponding to the maximum swelled volume of the total coated layers (in particular, not more than the amount obtained by subtracting the weight of the total coated layers from the weight of the solvent corresponding to the maximum swelled volume of the total coated layers).
  • a solvent for example, the method described in JP-A-61-147244, page 26.
  • the solvent may be previously incorporated in the light-sensitive material and/or the dye-fixing material in the form of being encapsulated in microcapsules, etc.
  • a system of incorporating a hydrophilic thermal solvent which is solid at room temperature but is melted at high temperature in the light-sensitive material or the dye-­fixing material may be employed.
  • the hydrophilic thermal solvent may exist in either the light-sensitive material or the dye-fixing material or in both the light-sensitive material and the dye-fixing material.
  • the layer containing the hydrophilic thermal solvent may be an emulsion layer or emulsion layers, an interlayer, a protective layer, or a dye-fixing layer but it is preferred that the solvent is incorporated in the dye-fixing layer and/or a layer adjacent to the dye-­fixing layer.
  • hydrophilic thermal solvent examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and heterocyclics.
  • a high-­boiling organic solvent may be incorporated in the light-sensitive material and/or the dye-fixing material.
  • a heating method in the heat development step and/or the dye transfer step there are a method of contacting with a heated block or plate, a method of contacting with a hot plate, a hot pressor, a heat roller, a halogen lamp heater, or an infrared or far infrared lamp heater, and a method of passing through a high-temperature atmosphere.
  • JP-A-U means an "unexamined published Japanese utility model application"
  • Emulsion (I) for Layer 5 (5th layer) was prepared as follows.
  • aqueous gelatin solution prepared by adding 20 g of gelatin, 3 g of potassium bromide, and 0.3 g of HO(CH2)2S(CH2)2S(CH2)2OH to 800 ml of water and keeping the solution at 55°C
  • solution (1) and solution (2) shown below were simultaneously added to the mixture over a period of 30 minutes.
  • solution (3) and solution (4) shown below were simultaneously added to the mixture over a period of 20 minutes.
  • the dye solution shown below was added to the mixture over a period of 18 minutes.
  • Emulsion (II) for Layer 3 was prepared as follows.
  • the emulsion was chemically sensitized at 60.0°C.
  • 1.6 mg of triethylthiourea and 100 mg of 4-hydroxy-6-methyl-1,3,3a-7-tetraazaindene were used and the ripening time was 55 minutes. Also, the amount of the emulsion obtained was 635 g.
  • Emulsion (III) for Layer 1 was prepared as follows. To an aqueous gelatin solution (prepared by adding 20 g of gelatin, 1 g of potassium bromide, and 0.5 g of HO(CH2)2S(CH2)2OH to 800 ml of water and keeping the solution at 50°C) were simultaneously added solution (I ⁇ ), solution (II ⁇ ) and solution (III ⁇ ) shown below with stirring vigorously at an equivalent flow rate over a period of 30 minutes. Thus, a dye-adsorbed mono­disperse silver bromide emulsion having a mean grain size of 0.42 ⁇ m was prepared.
  • a dispersion of zinc hydroxide was prepared as follows.
  • a dispersion of active carbon was prepared as follows.
  • gelatin dispersions of the following dye-­providing compounds, respectively, were prepared as follows.
  • each of the yellow, magenta, and cyan dye-­providing compounds shown below was added to 50 ml of ethyl acetate together with the components shown below and the mixture was heated to about 60°C to form each homogeneous solution. After adding 100 g of an aqueous 10% lime-processed gelatin solution, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water to each solution thus prepared with stirring, the resultant mixture was dispersed by a homogenizer at 10,000 r.p.m. for 10 minutes.
  • the dispersion is called a gelatin dispersion of a dye-providing compound.
  • the solution was mixed with 100 g of an aqueous solution of 10% lime-processed gelatin, 0.25 g of sidium hydrogensulfite, 0.3 g of sodium dodecylbenzene­sulfonate, and 30 ml of water with stirring and the mixture was dispersed by a homogenizer at 10,000 r.p.m. for 10 minutes.
  • the dispersion is called as a gelatin dispersion of electron donor (3)
  • a multilayer heat-developable color photographic light-sensitive material 101 having the following layers was prepared using the aforesaid emulsion and dispersion.
  • the compounds used are as follows.
  • Back Layer 1 Gelatin 3.25 g/m2 Hardening Agent (1) 0.25 " Back Layer 2 Gelatin 0.44 g/m2 Silicone Oil (1) 0.08 " Surface Active Agent (4) 0.04 " Surface Active Agent (5) 0.01 " Matting Agent (2) 0.03 " Structure of Support Layer Composition Layer Thickness ( ⁇ m) Surface Undercoat Layer Gelatin 0.1 Surface PE Layer (Glossy) Low-density Polyethylene: 89.2 parts 45.0 (Density: 0.923) Surface-treated Titanium Oxide: 10.0 parts Ultramarine: 0.8 part Pulp Layer Best Quality Paper (LBKP/NBKP 1:1, Density: 1.080) 92.6 Back PE Layer (Mat) High-density Polyethylene 36.0 (Density: 0.960) Back Undercoat Layer Gelatin 0.05 Colloidal Silica 0.05 Total 173.8
  • the compounds used for the dye-fixing material are as follows.
  • additives were added in the following manners. That is, when added in Layer 1, 3 or 5, it was added in a high-boiling solvent during preparation of gelatin dispersion of each dye-providing compound; when added in Layer 2 or 4, it was added in a high-boiling solvent during preparation of gelatin dispersion of electron donor for an interlayer; and when added in Layer 6, it was added as a gelatin dispersion of it alone.
  • Each of the aforesaid color photographic light­sensitive materials 101 to 120 was exposed to a tungsten lamp for 1/10 second at 5,000 lux through a blue (B), green (G), red (R), or grey color separation filter having continuously changing densities.
  • the assembly was heated for 15 seconds using a heat roller having controlled temperature such that the temperature of the water-absorbed layers became 85°C. Then, the image-receiving material was separated from the light-sensitive material, whereby clear blue, green, red, and grey images were formed on the image-receiving material without unevenness corresponding to the B, G, R, and grey separation filter.
  • a color photographic light-sensitive material 201 having the multilayer structure shown below was prepared using the same silver halide emulsions and the same dye-providing compounds as in the color photo­graphic light-sensitive material 101 in Example 1.
  • additives used were the same as those for the light-sensitive material 101 unless otherwise indicated.
  • organic silver salt emulsion was prepared as follows.
  • the antifoggant precursor (14) shown below was used in an amount of 0.2 mole times the amount of the dye-providing compound and was used together with the dye-providing compound and the electron donor as the oil dispersion as in Example 1.
  • Base Precursor (13) 0.30 Layer 5 Blue-Sensitive Emulsion Layer Emulsion (III) 0.30 g/m2 as silver Organic Silver Salt Emulsion 0.25 g/m2 Gelatin 1.00 "
  • Antifoggant Precursor (14) 0.07 " Yellow Dye-Providing Compound (1) 0.50 g/m2 High-Boiling Organic Solvent (1) 0.75 " Electron Donor (ED-12) 0.35 " Surface Active Agent (7) 0.05 " Electron Transfer Agent (X-5) 0.04 " Thermal Solvent (15) 0.20 " Hardening Agent (9) 0.01
  • Antifoggant Precursor (14) Thermal Solvent (15) Benzenesufonamide Base Precursor (13) Guanigine 4-Chlorophenylosufonylacetate Reducing Agent (16)
  • the light-sensitive material After exposing each of the light-sensitive materials thus prepared by the same manner as in Example 1, the light-sensitive material was uniformly heated on a heat block heated to 140°C for 30 seconds.
  • the aforesaid light-sensitive material thus heated was superposed to the dye-fixing material such that the layers were in contact relation with each other.
  • the dye-fixing material was separated from the light-­sensitive material. In each case, positive images having good discrimination were obtained on the dye-­fixing material.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP90114284A 1989-08-01 1990-07-25 Wärmeentwickelbares farbphotographisches lichtempfindliches Material Expired - Lifetime EP0411466B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1199645A JPH0363648A (ja) 1989-08-01 1989-08-01 熱現像カラー感光材料
JP199645/89 1989-08-01

Publications (3)

Publication Number Publication Date
EP0411466A2 true EP0411466A2 (de) 1991-02-06
EP0411466A3 EP0411466A3 (en) 1991-04-24
EP0411466B1 EP0411466B1 (de) 1995-12-13

Family

ID=16411298

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90114284A Expired - Lifetime EP0411466B1 (de) 1989-08-01 1990-07-25 Wärmeentwickelbares farbphotographisches lichtempfindliches Material

Country Status (4)

Country Link
US (1) US5079137A (de)
EP (1) EP0411466B1 (de)
JP (1) JPH0363648A (de)
DE (1) DE69024124T2 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0426087A2 (de) * 1989-10-30 1991-05-08 Fuji Photo Film Co., Ltd. Material zur Fixierung von Farbstoffen
WO2011113886A1 (fr) * 2010-03-18 2011-09-22 Rhodia Operations Nouveaux composes de type esteramide, leurs procedes de preparation et leurs utilisations

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05165139A (ja) * 1991-12-17 1993-06-29 Konica Corp 色素画像形成方法
US5420339A (en) * 1993-11-22 1995-05-30 Warner-Lambert Company Alpha-aryl or heteroaryl-substituted amide ester ACAT inhibitors
US5445913A (en) * 1994-02-25 1995-08-29 Eastman Kodak Company Process for the formation of heat image separation elements of improved sensitometry
JP2004148807A (ja) 2002-10-09 2004-05-27 Fuji Photo Film Co Ltd インクジェット記録方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555476A (en) * 1983-03-30 1985-11-26 Fuji Photo Film Co., Ltd. Heat development process with stabilizer
JPS61209444A (ja) * 1985-02-26 1986-09-17 Fuji Photo Film Co Ltd 画像形成方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59154445A (ja) * 1983-02-23 1984-09-03 Fuji Photo Film Co Ltd 画像形成方法
JPS60230134A (ja) * 1984-04-27 1985-11-15 Fuji Photo Film Co Ltd 熱現像感光材料
US4783396A (en) * 1985-10-31 1988-11-08 Fuji Photo Film Co., Ltd. Silver halide photographic materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4555476A (en) * 1983-03-30 1985-11-26 Fuji Photo Film Co., Ltd. Heat development process with stabilizer
JPS61209444A (ja) * 1985-02-26 1986-09-17 Fuji Photo Film Co Ltd 画像形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 40 (P-544)(2487) 05 February 1987, & JP-A-61 209444 (FUJI PHOTO FILM) 17 September 1986, *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0426087A2 (de) * 1989-10-30 1991-05-08 Fuji Photo Film Co., Ltd. Material zur Fixierung von Farbstoffen
EP0426087B1 (de) * 1989-10-30 1997-01-22 Fuji Photo Film Co., Ltd. Material zur Fixierung von Farbstoffen
WO2011113886A1 (fr) * 2010-03-18 2011-09-22 Rhodia Operations Nouveaux composes de type esteramide, leurs procedes de preparation et leurs utilisations
FR2957596A1 (fr) * 2010-03-18 2011-09-23 Rhodia Operations Nouveaux composes de type esteramide, leurs procedes de preparation et leurs utilisations

Also Published As

Publication number Publication date
DE69024124D1 (de) 1996-01-25
EP0411466A3 (en) 1991-04-24
JPH0363648A (ja) 1991-03-19
DE69024124T2 (de) 1996-06-13
US5079137A (en) 1992-01-07
EP0411466B1 (de) 1995-12-13

Similar Documents

Publication Publication Date Title
US5051335A (en) Heat developable light-sensitive material with paper support
US5270155A (en) Dye diffusion transfer type heat developable color light-sensitive material
EP0451833A1 (de) Farbphotographisches, silberhalogenidhaltiges Diffusionsmaterial
US5026634A (en) Color light-sensitive material
US5017454A (en) Heat-developable color light-sensitive material
EP0461416A2 (de) Photoempfindliches Farbdiffusionübertragungsmaterial
JP2893152B2 (ja) 熱現像感光材料
US5079137A (en) Heat-developable color photographic light-sensitive material
EP0353724A1 (de) Wärmeentwickelbares photoempfindliches Material
US5032487A (en) Color light-sensitive material
US5051348A (en) Heat-developable color light-sensitive material
US4968598A (en) Heat developable color light-sensitive material
US5316886A (en) Heat developable photosensitive materials
US5401622A (en) Thermally developable color photosensitive materials with U.V. absorbers
US5156939A (en) Heat-developable light-sensitive material
JP2881061B2 (ja) 熱現像カラー感光材料
JP2519964B2 (ja) 色素固定材料
EP0357040B1 (de) Wärmeentwickelbares photographisches Farbmaterial und Bildherstellungsverfahren damit
JP2579196B2 (ja) 熱現像カラー感光材料
JP2612206B2 (ja) カラー感光材料
EP0418743A2 (de) Wärmeentwickelbares lichtempfindliches Material
JPH0248659A (ja) 熱現像カラー感光材料
JPH04217243A (ja) 熱現像カラー感光材料
JPH04255845A (ja) 熱現像カラー感光材料
JPH0268547A (ja) 熱現像カラー感光材料

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB IT NL

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB IT NL

17P Request for examination filed

Effective date: 19910605

17Q First examination report despatched

Effective date: 19940621

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 19951213

Ref country code: FR

Effective date: 19951213

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19951213

REF Corresponds to:

Ref document number: 69024124

Country of ref document: DE

Date of ref document: 19960125

EN Fr: translation not filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20080807

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080806

Year of fee payment: 19

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090725

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100202